Dyeing formulations

ABSTRACT

The invention concerns dyeing formulations consisting of the following elements: a) at least a dye selected from the group comprising hardly water-soluble dyes a1) and water-soluble dyes a2), b) water, c) in the case of hardly water-soluble dyes a1), at least a dispersant and d) at least a compound of formula (I), wherein the variables are defined as follows: R 1 , R 2  are selected independently of each other from the group consisting of hydrogen, C 1 -C 4  alkyl, CH 2 —O—R 3 , R 3  representing hydrogen or C 1 -C 4  alkyl.

The present invention relates to colorant preparations comprising

a) at least one colorant selected from sparingly water-soluble colorantsa1) and water-soluble dyes a2),

b) water,

c) at least one dispersant in the case of substantially water-insolubleor sparingly water-soluble colorants a1), and

d) at least one compound of the general formula I

where

R¹ and R² are independently selected from

hydrogen,

C₁-C₄-alkyl and

CH₂—O—R³, where

R³ is hydrogen or C₁-C₄-alkyl.

The invention further relates to the use of these colorant preparationsas inks for the ink jet process and to a process for printing sheetlikeor three-dimensionally configured substrates in the ink jet process byusing these colorant preparations.

Inks for use in the ink jet process (such as Thermal Ink Jet, Piezo InkJet, Continuous Ink Jet, Valve Jet) have to meet a whole series ofdemanding technical requirements. They have to have a viscosity andsurface tension suitable for printing, they have to be stable instorage, ie they should not coagulate or flocculate, and they must notlead to cloggage of the printer nozzle, which can be problematicalespecially in the case of inks containing dispersed, ie undissolved,colorant particles.

Stability in storage further requires of these inks that the dispersedcolorant particles do not sediment. Finally, in the case of continuousink jet the inks shall be stable to the addition of conducting salts andbe free from any tendency to flock out with an increase in the ioncontent. In addition, the prints obtained have to meet colorists'requirements, ie show brilliance and depth of shade, and have goodfastnesses, for example rubfastness, lightfastness, waterfastness andwetrubfastness, and good drying characteristics.

WO 99/01516 discloses pigmented ink jet inks whose start-of-printcapability and storability are still in need of improvement.

EP-A 1 088 860 discloses aqueous inks which, in addition to a pigment,contain a compound of the general formula II a or II b

where each R, which may be the same or different, is hydrogen, methyl orethyl. However, the storability of the disclosed inks is still notsufficient for some purposes.

It is an object of the present invention to provide novel colorantpreparations having advantageous application properties in the ink jetprocess in that they in particular combine good start-of-print andsustained use performance with a good dry time.

We have found that this object is achieved by the colorant preparationsdefined at the beginning.

The colorant preparations according to the invention may includesparingly water-soluble, dispersed colorant a1) (finely divided organicor inorganic pigments or colorants which are substantially insoluble inthe water-solvent mixture) or dissolved colorant a2) (dyes which aresoluble in the water-solvent mixture). It will be appreciated that thecolorant preparations according to the invention may also includecolorant mixtures, but preferably only one colorant is present.Preference is given to colorant preparations according to the inventionthat are based on pigment. By way of brightening agent, these pigmentpreparations may include dyes which are similar to the pigment in hue,especially direct, acid or reactive dyes.

There now follow examples of suitable pigments a1), although vat dyesare recited as well because of the overlap with organic pigments.

Organic pigments: monoazo pigments: C.I. Pigment Brown 25; C.I. PigmentOrange 5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22,23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3,57:1, 63, 112, 146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1,3, 73, 74, 65, 97, 151 and 183; disazo pigments: C.I. Pigment Orange 16,34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;anthanthrone pigments: C.I. Pigment Red 168 (C.I. Vat Orange 3);anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. PigmentViolet 31; anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I.Pigment Violet 31; anthrapyrimidine pigments: C.I. Pigment Yellow 108(C.I. Vat Yellow 20); quinacridone pigments: C.I. Pigment Red 122, 202and 206; C.I. Pigment Violet 19; quinophthalone pigments: C.I. PigmentYellow 138; dioxazine pigments: C.I. Pigment Violet 23 and 37;flavanthrone pigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1);indanthrone pigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64(C.I. Vat Blue 6); isoindoline pigments: C.I. Pigment Orange 69; C.I.Pigment Red 260; C.I. Pigment Yellow 139 and 185; isoindolinonepigments: C.I. Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I.Pigment Yellow 109, 110, 173 and 185; isoviolanthrone pigments: C.I.Pigment Violet 31 (C.I. Vat Violet 1); metal complex pigments: C.I.Pigment Yellow 117, 150 and 153; C.I. Pigment Green 8; perinonepigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment Red194 (C.I. Vat Red 15); perylene pigments: C.I. Pigment Black 31 and 32;C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190 (C.I. Vat Red29) and 224; C.I. Pigment Violet 29; phthalocyanine pigments: C.I.Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16; C.I. Pigment Green7 and 36; pyranthrone pigments: C.I. Pigment Orange 51; C.I. Pigment Red216 (C.I. Vat Orange 4); thioindigo pigments: C.I. Pigment Red 88 and181 (C.I. Vat Red 1); C.I. Pigment Violet 38 (C.I. Vat Violet 3);triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. PigmentGreen 1; C.I. Pigment Red 81, 81:1 and 169; C.I. Pigment Violet 1, 2, 3and 27; C.I. Pigment Black 1 (aniline black);

C.I. Pigment Yellow 101 (aldazine yellow);

C.I. Pigment Brown 22;

vat dyes (in addition to those already mentioned above):

C.I. Vat Yellow 2, 3, 4, 5, 9, 10, 12, 22, 26, 33, 37, 46, 48, 49 and50;

C.I. Vat Orange 1, 2, 5, 9, 11, 13, 15, 19, 26, 29, 30 and 31;

C.I. Vat Red 2, 10, 12, 13, 14, 16, 19, 21, 31, 32, 37, 41, 51, 52 and61;

C.I. Vat Violet 2, 9, 13, 14, 15, 17 and 21;

C.I. Vat Blue 1 (C.I. Pigment Blue 66), 3, 5, 10, 12, 13, 14, 16, 17,18, 19, 20, 22, 25, 26, 29, 30, 31, 35, 41, 42, 43, 64, 65, 66, 72 and74;

C.I. Vat Green 1, 2, 3, 5, 7, 8, 9, 13, 14, 17, 26, 29, 30, 31, 32, 33,40, 42, 43, 44 and 49;

C.I. Vat Brown 1, 3, 4, 5, 6, 9, 11, 17, 25, 32, 33, 35, 38, 39, 41, 42,44, 45, 49, 50, 55, 57, 68, 72, 73, 80, 81, 82, 83 and 84;

C.I. Vat Black 1, 2, 7, 8, 9, 13, 14, 16, 19, 20, 22, 25, 27, 28, 29,30, 31, 32, 34, 36, 56, 57, 58, 63, 64 and 65;

inorganic pigments: white pigments: titanium dioxide (C.I. Pigment White6), zinc white, pigment grade zinc oxide; zinc sulfide, lithopone; leadwhite; black pigments: iron oxide black (C.I. Pigment Black 11), ironmanganese black, spinell black (C.I. Pigment Black 27); carbon black(C.I. Pigment Black 7); color pigments: chromium oxide, chromium oxidehydrate green; chrome green (C.I. Pigment Green 48); cobalt green (C.I.Pigment Green 50); ultramarine green; cobalt blue (C.I. Pigment Blue 28and 36); ultramarine blue; iron blue (C.I. Pigment Blue 27); manganeseblue; ultramarine violet; cobalt violet, manganese violet; iron oxidered (C.I. Pigment Red 101); cadmium sulfoselenide (C.I. Pigment Red108); molybdate red (C.I. Pigment Red 104); ultramarine red; iron oxidebrown, mixed brown, spinell and corundum phases (C.I. Pigment Brown 24,29 and 31), chrome orange; iron oxide yellow (C.I. Pigment Yellow 42);nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157and 164); chrome titanium yellow; cadmium sulfide and cadmium zincsulfide (C.I. Pigment Yellow 37 and 35); chrome, yellow (C.I. PigmentYellow 34), zinc yellow, alkaline earth metal chromates; Naples yellow;bismuth vanadate (C.I. Pigment Yellow 184); interference pigments:metallic effect pigments based on coated metal platelets; pearl lusterpigments based on mica platelets coated with metal oxide, liquid crystalpigments.

Preferred pigments in this context are monoazo pigments (especiallylaked BONS pigments, naphthol AS pigments), disazo pigments (especiallydiaryl yellow pigments, bisacetoacetanilide pigments, disazopyrazolonepigments), quinacridone pigments, quinophthalone pigments, perinonepigments, phthalocyanine pigments, triarylcarbonium pigments (alkaliblue pigments, laked rhodamines, dye salts with complex anions),isoindoline pigments and carbon blacks.

Specific examples of particularly preferred pigments are: C.I. PigmentYellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. PigmentBlue 15:3 and 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and43 and C.I. Pigment Green 7.

These pigments are advantageously useful for preparing ink jet ink setsbased on the colorant preparations according to the invention. The levelof the particular pigments in the individual inks must be adapted to theparticular requirements (trichromatic coloration, for example).

The following pigment combinations are particularly commendable:

C.I. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3and C.I. Pigment Black 7;

C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or15:4 and C.I. Pigment Black 7;

C.I. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3,C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I. Pigment Green 7;

C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5 and C.I. Pigment Green7;

C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or15:4, C.I. Pigment Black 7, C.I. Pigment Orange 38 and C.I. PigmentGreen 7;

C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or15:4, C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I. PigmentGreen 7.

Useful dyes a1), which are substantially insoluble in the water-solventmixture, as well as the vat dyes already mentioned, include inparticular azo, anthraquinone, quinophthalone, benzodifuran, methine andazamethine dyes that are free of acidic or ionic groups.

Useful dyes a1) include specifically for example:

C.I. Disperse Yellow 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 11:1, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31,32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49,50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67,68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85,86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102,103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116,117, 118, 119, 120, 121, 179, 180, 181, 182, 183, 184, 184:1, 198, 200,201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214,215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227 and 228;

C.I. Disperse Orange 1, 2, 3, 3:3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 25:1, 26, 27, 28, 29, 30,31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 41:1, 42, 43, 44, 45, 46,47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82,83, 84, 85, 86, 87, 88, 89, 90, 91, 126, 127, 128, 129, 130, 131, 136,137, 138, 139, 140, 141, 142, 143, 145, 146, 147 and 148;

C.I. Disperse Red 1, 2, 3, 4, 5, 5:1, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 30:1,31, 32, 33, 34, 35, 36, 38, 39, 40, 41, 43, 43:1, 46, 48, 50, 51, 52,53, 54, 55, 55:1, 56, 58, 59, 60, 61, 63, 65, 66, 69, 70, 72, 73, 74,75, 76, 77, 79, 80, 81, 82, 84, 85, 86, 86:1, 87, 88, 89, 90, 91, 92,93, 94, 96, 97, 98, 100, 102, 103, 104, 105, 106, 107, 108, 109, 110,111, 112, 113, 115, 116, 117, 118, 120, 121, 122, 123, 125, 126, 127,128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141,142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 151:1, 152, 153, 154,155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 167:1,168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181,182, 183, 184, 185, 186, 187, 188, 189, 190, 190:1, 191, 191:1, 192,193, 194, 195, 211, 223, 224, 273, 274, 275, 276, 277, 278, 279, 280,281, 302:1, 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315, 316,317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330,331, 332, 333, 334, 335, 336, 338, 339, 340, 341, 342, 343, 344, 346,347, 348, 349, 352, 356 and 367;

C.I. Disperse Violet 1, 2, 3, 4, 4:1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 33, 34,35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52,53., 54, 55, 56, 57, 58, 59, 60, 70, 81, 86, 87, 88, 89, 91, 92, 93, 94,96 and 97;

C.I. Disperse Blue 1, 1:1, 2, 3, 3:1, 4, 5, 6, 7, 7:1, 8, 9, 10, 11, 12,13, 13:1, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 23:1, 24, 25, 26, 27,28, 29, 30, 31, 32, 33, 34, 35, 36, 38, 39, 40, 42, 43, 44, 45, 47, 48,49, 51, 52, 53, 54, 55, 56, 58, 60, 60:1, 61, 62, 63, 64, 64:1, 65, 66,68, 70, 72, 73, 75, 76, 77, 79, 80, 81, 81:1, 82, 83, 84, 85, 86, 87,88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104,105, 106, 107, 108, 109, 111, 112, 113, 114, 115, 116, 117, 118, 119,121, 122, 123, 124, 125, 126, 127, 128, 130, 131, 132, 133, 134, 136,137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150,151, 152, 153, 154, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165,165:2, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 195, 281, 282,283, 283:1, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 316,317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330,331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344,345, 346, 347, 349, 351 and 359;

C.I. Disperse Green 1, 2, 5, 6 and 9;

C.I. Disperse Brown 1, 2, 3, 4, 4:1, 5, 7, 8, 9, 10, 11, 18, 19, 20 and21;

C.I. Disperse Black 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20,22, 24, 25, 26, 27, 28, 29, 29:1, 30, 31, 32, 33, 34 and 36;

C.I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25:1, 27,28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82,83, 83:1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130,131, 133, 135, 141, 143, 144, 145, 146, 157, 160:1, 161, 162, 163, 167,169, 172, 173, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189,190 and 191;

C.I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31A, 40:1, 41,45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105,106, 107, 108, 109, 110, 111, 112 and 113;

C.I. Solvent Red 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30,33, 35, 41, 42, 45, 48, 49, 52, 68, 69, 72, 73, 83:1, 84:1, 89, 90,90:1, 91, 92, 106, 109, 111, 118, 119, 122, 124, 125, 127, 130, 132,135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164:1, 165,166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207,208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234,235, 236, 238, 239, 240, 241, 242, 243, 244, 245, 247 and 248;

C.I. Solvent Violet 2, 8, 9, 11, 13, 14, 21, 21:1, 26, 31, 36, 37, 38,45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60 and 61;

C.I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45,48, 51, 58, 59, 59:1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98,99, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136,137, 138, 139 and 143;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35;

C.I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52,53, 59, 60, 61, 62 and 63;

C.I. Solvent Black 3, 5, 5:2, 7, 13, 22, 22:1, 26, 27, 28, 29, 34, 35,43, 45, 46, 48, 49 and 50.

Also suitable are the substituted benzodifuranone dyes which are knownper se and whose basic structure conforms to the formula A.

Such dyes may be substituted on either or both of the phenyl rings.Useful substituents X¹ and X² include halogen, alkyl with or withoutinterruption by nonadjacent oxygen atoms, alkoxy with or withoutinterruption by oxygen atoms and substitution in the alkyl moiety,hydroxyl, substituted or unsubstituted amino, cyano, nitro andalkoxycarbonyl.

Useful dyes further include dyes of the following formulae B to E:

Further examples of insoluble dyes a1) are recited in WO 97/46623, WO98/24850 and WO 99/29783.

The undissolved, dispersed colorant a1) should be very finely divided.It is preferred for 95% and more preferably 99% of the colorantparticles a1) to have an average particle diameter of 1 μm andpreferably 0.5 μm.

Useful dyes a2), which are soluble in the water-solvent mixture, includein particular arylmethane, azo, methine, rhodamine and metal complexdyes which contain acidic or ionic groups.

Examples of suitable dyes a2) are specifically:

C.I. Basic Yellow 2, 37, 78, 94, 96, 97, 98, 102 and 111;

C.I. Basic Orange 2, 60, 62 and 63;

C.I. Basic Red 1, 14, 49, 108 and 111;

C.I. Basic Violet 1, 3, 4, 10, 11, 49 and 50;

C.I. Basic Blue 26, 152, 157, 158 and 161;

C.I. Basic Green 1 and 4;

C.I. Basic Brown 1;

C.I. Acid Orange 7 and 8;

C.I. Acid Blue 9;

C.I. Direct Yellow 4, 5, 11, 15, 127, 131 and 147;

C.I. Direct Red 239 and 254;

C.I. Direct Blue 161, 199, 279 and 281;

C.I. Reactive Red 120.

The colorant preparations according to the invention generally includefrom 0.01 to 20% by weight, and preferably from 0.2 to 10% by weight andmore preferably from 1 to 6% by weight of colorant a), particularlysuitable amounts in the case of colorant a1) ranging from 1 to 6% byweight and in the case of colorant a2) ranging from 1 to 10% by weight.

Water is the main constituent b) of the colorant preparations accordingto the invention, preference being given to demineralized, completelyion-free water as obtainable for example through the use of an ionexchanger. The water content is customarily in the range from 50 to 95%by weight. The preparations according to the invention preferably have awater content of from 60 to 80% by weight. In fact, the water content ispreferably in the range from 60 to 80% by weight in the case ofbinder-free preparations and in the range from 50 to 75% by weight inthe case of binder-containing preparations.

When the colorant preparations according to the invention are based onundissolved colorants a1), they will generally include from 0.1 to 25%by weight and preferably from 0.5 to 10% by weight of at least onedispersant c). In the case of dissolved colorants a2), component c) iscustomarily omitted.

Useful dispersants c) include in principle all dispersants known foraqueous systems.

Particularly useful dispersants are water-soluble dispersants based onone or more water-soluble alkoxylated phenols C 1, one or morearylsulfonic acid-formaldehyde condensation products C 2, one or morecondensation products of an at least difunctional isocyanate withcompounds C 3 each bearing one isocyanate-reactive group or one or morealkoxylated hydroxynaphthalenes C 4.

Useful dispersants C 1 include alkoxylated phenols of the formula C 1a,

where

m is between 0 and 180, preferably between 0 and 125

n is between 10 and 180, n is preferably at least 25 and particularlypreferably at least 37, subject to the proviso that n≧m;

M is an alkali metal, preferably Na or K and particularly preferably Na;

r is 0 or 1, or mixtures thereof.

The compounds C 1a and C 1b are advantageously prepared by reacting thephenols C 1a.1 or C 1a.2

with propylene oxide and subsequently reacting the adduct with ethyleneoxide or by reacting C 1a.1 or C 1a.2 with ethylene oxide. The adductsmay subsequently be reacted with chlorosulfonic acid or sulfur trioxideto convert them completely or partially into acid sulfuric esters andthe resulting acid esters are neutralized with alkalis.

The phenols of the formulae C 1a.1 and C 1a.2 are obtainable by reactingbisphenol A (2,2-(p,p′-bishydroxydiphenyl)propane) or phenol withrespectively 4 or 2 mol of styrene in the presence of an acid as acatalyst. The phenols C 1a.1 and C 1a.2 are reacted according to knownprocesses first with propylene oxide and then with ethylene oxide oronly with ethylene oxide in the presence of acidic or alkalinecatalysts, for example NaOCH₃ or SbCl₅, to form the respectivecorresponding alkoxylation products C 1a and C 1b where r=0. Thealkoxylation may be carried out for example according to the processdescribed in U.S. Pat. No. 2,979,528.

The acid sulfuric esters are prepared by reaction of the alkoxylationproducts with chlorosulfonic acid or sulfur trioxide, the amount ofchlorosulfonic acid or sulfur trioxide being selected so that all thefree hydroxyl groups or only a certain portion thereof is sulfated. Thelatter case produces mixtures of compounds of the formulae C 1a and C1b, which contain free and sulfated hydroxyl groups. For use as adispersant, the as-synthesized acid esters of sulfuric acid areconverted into water-soluble salts. Advantageous water-soluble salts arethe alkali metal salts, for example the sodium or potassium salts. Forthis two equivalents of the basic compounds are required in the case ofchlorosulfonic acid, one equivalent in the case of sulfur trioxide. Thebasic compound used is advantageously an aqueous alkali metal hydroxide.The neutralization temperature should not exceed 70° C. The saltsobtained can be used in the form of aqueous solutions or else isolatedas such and used in solid form.

Preference is given to dispersants C 1 where m is from 0 to on average2.5, n is on average from 37 to 250 and r is on average from 0 to onaverage 0.5. Particular preference is given to dispersants C 1 where ais from 0 to on average 2.5, b is on average from 50 to 100 and d is onaverage 0.5.

The dispersants C 1 are known and described for example in U.S. Pat. No.4,218,218.

The dispersants C 2 are obtainable by sulfonation of aromatic compoundssuch as naphthalene itself or of naphthalene-comprising mixtures andsubsequent condensation of the resultant arylsulfonic acids withformaldehyde.

The preferred starting material for preparing the arylsulfonic acids wasthe mixture of aromatic compounds which is characterized in Table 1 andwhich was obtained by thermal cracking of a naphthenic residue oil atfrom 1400 to 1700° C. and fractionation of the cracking products(fraction which passes over at 1013 mbar and 100-120° C.). Thesenaphthenic residue oils are obtained in the cracking of light gasolineand are also referred to as high boiling aromatic hydrocarbon oils.

This aromatics fraction is a mixture of a multiplicity of aromaticsubstances whose structure and amount is practically impossible todetermine in any detail. The following aryl compounds are the mostimportant representatives of this aromatics fraction: TABLE 1 % byweight in aromatics fraction Naphthalene 30-55 2-Methylnaphthalene  5-151-Methylnaphthalene  4-10 Indene  3-10 Biphenyl 1-5 Methylindene 1-5Acenaphthene 1-4

The aromatics fraction further includes, in terms of identifiedconstituents, in amounts from 0.1 to about 2% by weight, the followingaromatic compounds: fluorene, indan, α-methylstyrene, phenanthrene,methylindan, dimethylnaphthalene, ethylnaphthalene, xylenes, tetralin,styrene, methylethylbenzene, anthracene, fluoranthrene, pyrene andtoluene.

The dispersant C 2 may be prepared in the presence of aromatic orlong-chain aliphatic carboxylic acids, their salts, anhydrides ormixtures.

Examples of suitable aromatic carboxylic acids and derivatives thereofare naphthalenecarboxylic acid, phthalic acid, terephthalic acid,isophthalic acid, benzoic acid, trimellitic acid, phenylacetic acid,phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid,diphenylacetic acid, m-hydroxybenzoic acid, benzenetetracarboxylic acidor acid anhydrides such as trimellitic anhydride,benzene-1,2,4,5-tetracarboxylic dianhydride or phthalic anhydride.

Suitable long-chain aliphatic carboxylic acids include in particularsaturated or olefinically unsaturated, linear or branched aliphaticmonocarboxylic acids having from 8 to 22, preferably from 8 to 18,carbon atoms of a natural or synthetic origin, for example higher fattyacids such as lauric acid, myristic acid, palmitic acid, stearic acid,oleic acid, linoleic acid or linolenic acid or synthetically producedcarboxylic acids such as 2-ethylhexanoic acid, isononanoic acid orisotridecanoic acid.

Suitable salts of the carboxylic acids mentioned are the alkali metal,ammonium or alkaline earth metal salts, said alkali metal, ammonium oralkaline earth metal salts being obtainable, for example, byneutralization of the corresponding carboxylic acids with sodiumhydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate,magnesium carbonate, calcium oxide, calcium hydroxide, ammonia oralkanolamines such as ethanolamine, diethanolamine or triethanolamine.

Preference is given to sodium benzoate, sodium phenylacetate, sodiumsalicylate, sodium 4-hydroxybenzoate, sodium terephthalate, sodium2-hydroxy-3-naphthalenecarboxylate, naphthalene-1-carboxylic acid,phthalic anhydride or benzoic acid.

Dispersants C 2 which are particularly suitable in this case comprisefrom 50 to 97% by weight, especially from 70 to 95% by weight, ofarylsulfonic acid-formaldehyde condensation products and from 3 to 50%by weight, especially from 5 to 30% by weight, of aromatic or long-chainaliphatic carboxylic acids, their salts or anhydrides or mixturesthereof.

These mixtures are initially sulfonated by reaction with concentratedsulfuric acid or with oleum having an SO₃ content of from 10 to 65% byweight at from 120-160° C. and preferably at 135-145° C. Per part byweight of the aromatics it is advantageous to use from 0.7 to 1.5 partsby weight of oleum having an SO₃ content of 65% by weight or acorresponding amount of oleum having a lower SO₃ content. The reactiontime is customarily in the range from 1.5 to 3 hours at 145° C., in therange from 2¼ to 4 hours at 140° C. and in the range from 3¼ to 6 hoursat 135° C.

After sulfonation, the arylsulfonic acid mixtures contain at least 50%by weight of a mixture of α- and β-naphthalenesulfonic acids, the ratioof the α- to the β-isomers being customarily in the range from 20:1 to1:8, especially in the range from 10:1 to 1:5 and most preferably in therange from 1:1 to 1:2.

The sulfonated products are subsequently condensed with formaldehyde.This is generally effected by diluting the reaction mixture of thesulfonation reaction with water and then adding formaldehyde, preferablyin the form of an aqueous solution from 10 to 50% by weight in strength.The mixture thus formed is maintained at from 90 to 105° C. for from 4to 12 and preferably from 7 to 9 hours. When elevated pressure isemployed, for example in the range from 1.1 to 10 bar, it is alsopossible to use reaction temperatures in the range from 105 to 150° C.It is customary to use from 0.05 to 0.2 and preferably from 0.07 to 0.17part by weight of formaldehyde, based on sulfonation products.

After the reaction has ended, the reaction mixture is customarilyneutralized, for example with sodium hydroxide, potassium hydroxide,calcium hydroxide, sodium carbonate, potassium carbonate or sodiumbicarbonate, in the form of the aqueous solutions, until the pH is inthe range from 6 to 11.

The condensation products obtained from the abovementioned aromaticsfraction have a sulfonic acid group content of not more than 40% byweight. The production process is such that the condensation productsmay additionally contain up to 10% by weight of Na₂SO₄ and up to 25 mol% of sulfuric acid, based on sulfonic acid groups.

The dispersants C 2 and their preparation are known; cf. for exampleU.S. Pat. No. 5,186,846, DE-A-11 37 005 or EP-A-380 778.

The dispersants C 3 are condensation products of at least difunctionalisocyanates, which serve as point of attachment, with a polymericcompound (hereinafter referred to as stabilizer block) which isterminated at one end by an isocyanate-reactive group and which makessolid particles to be dispersed compatible with the dispersion medium,and an anchor group block, which can be either a homo- or copolymer of anitrogenous monomer or a phosphonic ester, which each possess anisocyanate-reactive group and which each sorb onto the solid particlesto be dispersed.

The isocyanate connecting the stabilizer block and the anchor groupblock is a diisocyanate or a more highly functional polyisocyanatehaving an average NCO functionality of from 2.0 to 4.5.

The diisocyanates can be aromatic or aliphatic, preference being givento aliphatic diisocyanates, such as tetramethylene diisocyanate,hexamethylene diisocyanate, octamethylene diisocyanate, decamethylenediisocyanate, dodecamethylene diisocyanate, tetradecamethylenediisocyanate, trimethylhexane diisocyanate or tetramethylhexanediisocyanate, 1,4-, 1,3- or 1,2-diisocyanatocyclohexane,4,4′-di(isocyanatocyclohexyl)-methane,1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophoronediisocyanate) or 2,4- or 2,6-diisocyanato-1-methylcyclohexane,particular preference being given to hexamethylene diisocyanate andisophorone diisocyanate.

The higher polyisocyanates may likewise be aromatic or aliphatic. Heretoo preference is given to aliphatic polyisocyanates, especially thosehaving an average NCO functionality of from 1.7 to 5, especially about3. The following groups are mentioned by way of example:

(a) Isocyanurate group containing polyisocyanates of aliphatic and/orcycloaliphatic diisocyanates. Particular preference is given here to thecorresponding isocyanato-isocyanurates based on hexamethylenediisocyanate and isophorone diisocyanate. These isocyanurates are inparticular simple trisisocyanatoalkyl or trisisocyanatocycloalkylisocyanurates, which are cyclic trimers of the diisocyanates, ormixtures with their higher homologs containing more than oneisocyanurate ring. The isocyanato-isocyanurates generally have an NCOcontent of from 10 to 30% by weight, in particular from 15 to 25% byweight, and an average NCO functionality of from 2.6 to 4.5.

(b) Uretdione diisocyanates having aliphatically and/orcycloaliphatically attached isocyanate groups, which are preferablyderived from hexamethylene diisocyanate or isophorone diisocyanate.Uretdione diisocyanates are cyclic dimerization products ofdiisocyanates.

(c) Biuret group containing polyisocyanates having aliphaticallyattached isocyanate groups, especially tris(6-isocyanato-hexyl)biuret orits mixtures with its higher homologs. These biuret group containingpolyisocyanates generally have an NCO content of from 18 to 25% byweight and an average NCO functionality of from 3 to 4.5.

(d) Urethane and/or allophanate group containing polyisocyanates havingaliphatically or cycloaliphatically attached isocyanate groups, as areobtainable for example by reaction of excess amounts of hexamethylenediisocyanate or of isophorone diisocyanate with simple polyhydricalcohols, such as trimethylolpropane, glycerol, 1,2-dihydroxypropane ormixtures thereof. These urethane and/or allophanate group containingpolyisocyanates generally have an NCO content of from 12 to 20% byweight and an average NCO functionality of from 2.5 to 3.

(e) Oxadiazinetrione group containing polyisocyanates, preferablyderived from hexamethylene diisocyanate or isophorone diisocyanate. Suchoxadiazinetrione group containing polyisocyanates are preparable fromdiisocyanate and carbon dioxide.

(f) Uretoneimine-modified polyisocyanates.

The polymeric compound forming the stabilizer block is preferably apolymeric compound of the general formula C 3aR⁵—Y_(x)—XH   C 3awhere

R⁵ is hydrogen,

C₁-C₂₈-alkyl, preferably C₁-C₁₀-alkyl, for example methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl,iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl,n-nonyl and n-decyl; preferably C₁-C₆-alkyl such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethyl-propyl,iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferablyC₁-C₄-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, sec-butyl and tert-butyl.

C₂-C₂₈-alkenyl having one or more double bonds, substituted orunsubstituted, for example vinyl, 1-allyl, 3-allyl, ω-butenyl,ω-pentenyl, ω-hexenyl, ω-decenyl, ω-undecenyl, ω-eicosenyl,1-cis-buta-1,3-dienyl or 1-cis-hexa-1,5-dienyl. Examples of substitutedC₂-C₂₈-alkenyl groups are isopropenyl, 1-isoprenyl, α-styryl, β-styryl,1-cis-1,2-phenylethenyl or 1-trans-1,2-phenylethenyl.

C₂-C₂₈-alkynyl having one or more triple bonds, substituted orunsubstituted and optionally having double bonds, for example ethynyl,propargyl, ω-butynyl, but-2-ynyl, ω-pentynyl, pent-2-ynyl, pent-3-ynyl,2-methylpent-3-ynyl, ω-hexynyl, ω-decynyl, ω-undecynyl, ω-eicosynyl,

or the residue of a polymerization initiator or of a chain regulator,

Y represents identical or different polymerized units of monomersselected from the group consisting of α,β-ethylenically unsaturatedmono- or-dicarboxylic acids; unsubstituted or hydroxyl-, C₁-C₆-alkoxy-,polyalkylenoxy- or halogen-mono- or -polysubstituted C₁-C₂₀-(cyclo)alkylor C₇-C₂₀-aralkyl esters, amides, nitriles or anhydrides ofα,β-ethylenically unsaturated mono- or dicarboxylic acids; vinyl orallyl esters of aliphatic or aromatic carboxylic acids; vinyl or allylethers; ethylenically unsaturated sulfonic acids or sulfonic acidderivatives, halogenated or unhalogenated ethylenically unsaturatedaliphatic C₂-C₂₀ hydrocarbons; aromatic ethylenically unsaturatedcompounds and compounds polymerizable to form polyphosphacenes; or is

where

R⁶ to R⁹ are independently hydrogen,

C₁-C₆-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl,neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,particularly preferably C₁-C₄-alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

C₆-C₂₀-aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, particularly preferably phenyl,

—CH₂—Cl or —CH₂—OH,

and Y¹, Y² are independently a C₂-C₂₀-alkylene, C₆-C₁₄-arylene such asfor example p-phenylene or m-phenylene or aralkylene group,

x is an integer between 0 and 10,000, preferably 3 2, especially 3 3 andparticularly preferably in the range from 30 to 1000, and

X is COO, O, S or NR¹⁰, where R¹⁰ is H or a C₁-C₆-alkyl group as definedabove.

The polymeric compound C 3a is preferably constructed using C₁-C₈-alkyl(meth)acrylates. Particular preference is given to polymerizing one ormore C₁-C₄-alkyl methacrylates, especially methyl methacrylate and/orbutyl methacrylate. The isocyanate-reactive group XH is preferably ahydroxyl group which may be introduced into the terminal position of thepolyacrylate with the aid of initiators which provide a hydroxyl freeradical on decomposition and/or with the aid of chain regulators whichcontain a hydroxyl group.

The polymeric compound C 3a is most preferably a mono(generally C₁-C₁₈,preferably C₁-C₄)alkyl ether of a poly (especially C₂-C₄)alkyleneglycol, which may be obtained for example by reacting an alkanol with analkene oxide, such as ethylene oxide, propylene oxide and butyleneoxide, or epichlorohydrin. Of particular suitability are C₁-C₁₈(especially C₁-C₄) alkanols alkoxylated with from 5 to 10,000,preferably from 5 to 80, mol of ethylene oxide and/or propylene oxide,and polyethylene glycol monomethyl ethers are very particularly useful.

The weight average molecular weight of the stabilizer block ispreferably within the range from about 250 to 100,000, especially withinthe range from about 500 to 7000.

An anchor group block embodiment useful for constructing the dispersantc3) is based on homo- or copolymers of one or more monomers selectedfrom the group consisting of N-vinylamides, N-vinyllactams and vinyl-orallyl-substituted nitrogenous heterocycles. Examples of particularlyuseful monomers are N-vinylpyrrolidone, N-vinylpyridine,N-vinylcaprolactam, N-vinylimidazole and N-vinylformamide, of whichN-vinyl-pyrrolidone is preferred. The homo- or copolymer preferably hasa K value of from 10 to 100, especially from 10 to 30. Termination inthe form of a hydroxyl group as isocyanate-reactive group may beaccomplished by conducting the polymerization in water or a loweralcohol such as isopropanol or by polymerization in the presence of anappropriate chain regulator and/or initiator.

A further anchor group block embodiment useful for constructing thedispersant c3) is formed by phosphonic esters of the general formula C3b

where

R¹¹ and R¹² are independently C₁-C₄-alkyl such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl,especially R¹¹=R¹²=methyl or ethyl;

Q is NR_((2-p)) or CR_((3-p)) (R═H or C₁-C₈-alkyl);

Y³ and Y⁴ are independently a chemical bond or unsubstituted orC₁-C₈-alkyl- or aryl-substituted C₁-C₁₀-alkylene with or withoutinterruption by one or more O, NR, CO, COO, OCO, CONR or NRCO;

p is 1 or 2; and

Y⁵ is COO, O, S or NR¹³, where R¹³ is H or a C₁-C₆-alkyl group asdefined above.

Preferred examples of these phosphonic esters are diethylN,N-bis(hydroxyethyl)aminomethylphosphonate, the dimethyl or diethylesters of 3-hydroxymethylamino-3-oxopropylphosphonic acid,3-aminopropylphosphonic acid, 1-aminopropylphosphonic acid,2-aminooctylphosphonic acid, 1-aminooctylphosphonic acid,1-aminobutylphosphonic acid, hydroxymethylphosphonic acid and1-hydroxyethylphosphonic acid.

The reaction of the di- or polyisocyanate with the stabilizer block andthe anchor group block can take place in two steps or in a one-potreaction. Preferably, however, the reaction takes place in two stepswhere the di- or polyisocyanate is reacted with the stabilizer block inthe first step. The reaction can take place in the absence or presenceof a solvent, preference being given to the reaction in the presence ofa solvent, such as acetone, THF, toluene, dioxane. When the stabilizerblock has been prepared by polymerization of an ethylenicallyunsaturated compound, the reaction of the stabilizer block with the di-or polyisocyanate can advantageously be carried out in the same solventas the free-radical polymerization. The reaction can be carried outwithout catalyst or preferably in the presence of a catalyst, such as atertiary amine, especially triethylamine, or a metal salt, especiallytin octoate or lead octoate, or an organometallic compound, such asdibutyltin dilaurate or titanium tetramethoxide. The reaction isgenerally carried out at a temperature from room temperature to 125° C.,especially within the range from 40 to 90° C.

Further details concerning dispersants C 3 are described in DE-A-198 42952.

Dispersants C 4 are alkoxylated hydroxynaphthalenes, preferablyethoxylated β-hydroxynaphthalenes. Dispersants c4) generally have anaverage molecular weight M_(w) of from 2000 to 40 000 g/mol, especiallyfrom 20 000 to 35 000 g/mol, and particularly from 25 000 to 30 000g/mol.

Dispersants C 4 are generally known and available in a customary mannerby alkoxylation of hydroxynaphthalene.

The colorant preparations according to the invention further include atleast one compound of the general formula I

where

R¹ and R² are independently selected from hydrogen, C₁-C₄-alkyl, forexample methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyland tert-butyl; CH₂—O—R³, where

R³ is hydrogen or C₁-C₄-alkyl selected from methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Preferably R¹ and R² are the same. Most preferably R¹ and R² are thesame and are each selected from hydrogen or methyl or CH₂OH.

Illustrative representatives of the compounds of the general formula Iare obtainable as follows:

Compound I a

is advantageously preparable in a known manner by condensing glyoxalwith one equivalent of urea in the presence of an alkali, as reportedfor example in R. Wegler et al., Methoden Org. Chem. (Houben-Weyl),volume 14/2, page 341, Thieme Verlag Stuttgart, 1963 and the referencescited therein.

Compound I b

is obtainable for example by adding two or more equivalents offormaldehyde under similar conditions. Alternatively, compound I b isobtainable by reacting glyoxal with formaldehyde and urea at pH 5.5 asdescribed in GB 1,273,517.

Compound I c

and other symmetrical and asymmetrical derivatives are obtainable by amethod from Russ. Chem. Bull. 1998, 47, 1561 and the references citedtherein.

The compounds of the general formula I are customarily obtained as anisomeric mixture of cis- and trans-diols. The present invention can beperformed using pure cis-diol, pure trans-diol or else isomericmixtures.

The compounds of the general formula I are customarily added in amountsfrom 0.1 to 20% by weight, based on the colorant preparation.

The colorant preparations according to the invention may include organicsolvents as a further component. Low molecular weightpolytetrahydrofuran is a preferred additive, and it can be used alone orpreferably in a mixture with one or more high-boiling water-soluble orwater-miscible organic solvents.

The polytetrahydrofuran whose use is preferred customarily has anaverage molecular weight M_(w) of from 150 to 500 g/mol, preferably from200 to 300 g/mol and particularly preferably of about 250 g/mol(corresponding to a molecular weight distribution of from 225 to 275g/mol; Poly-THF 25.0, BASF Aktiengesellschaft).

Polytetrahydrofuran is preparable in a conventional manner by cationicpolymerization of tetrahydrofuran. This produces linearpolytetramethylene glycols.

When polytetrahydrofuran is present in a mixture with further organicsolvents, the invention provides that the solvents used be high-boiling(ie, boiling point generally >100° C.) and hence water-retaining organicsolvents that are soluble in or miscible with water.

Useful solvents include polyhydric alcohols, preferably branched orunbranched polyhydric alcohols containing from 2 to 8, especially from 3to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propyleneglycol, glycerol, erythritol, pentaerythritol, pentitols such asarabitol, adonitol and xylitol and hexitols such as sorbitol, mannitoland dulcitol.

Useful solvents further include polyethylene glycols and polypropyleneglycols, which terms also comprehend the lower polymers (di-, tri- andtetramers), and their monoalkyl (especially C₁-C₆-alkyl and inparticular C₁-C₄-alkyl) ethers. Preference is given to polyethyleneglycols and polypropylene glycols having average molecular weights offrom 100 to 1500 g/mol, especially from 200 to 800 g/mol, in particularfrom 300 to 500 g/mol. Specific examples are di-, tri- and tetraethyleneglycol, diethylene glycol monomethyl, monoethyl, monopropyl andmonobutyl ethers, triethylene glycol monomethyl, monoethyl, monopropyland monobutyl ethers, di-, tri- and tetra-1,2- and -1,3-propylene glycoland di-, tri- and tetra-1,2- and -1,3-propylene glycol monomethyl,monoethyl, monopropyl and monobutyl ethers.

Useful solvents further include pyrrolidone and N-alkylpyrrolidoneswhose alkyl chain preferably contains from 1 to 4 and especially 1 or 2carbon atoms. Examples of useful alkylpyrrolidones areN-methylpyrrolidone, N-ethylpyrrolidone andN-(2-hydroxyethyl)pyrrolidone.

Examples of particularly preferred solvents are 1,2-propylene glycol,1,3-propylene glycol, glycerol, sorbitol, diethylene glycol,polyethylene glycol (M_(w) 300-500 g/mol), diethylene glycol monobutylether, triethylene glycol monobutyl ether, pyrrolidone,N-methylpyrrolidone and N-(2-hydroxyethyl)pyrrolidone.

Polytetrahydrofuran may also be mixed with one or more (eg two, three orfour) of the above-recited solvents.

The colorant preparations according to the invention generally includefrom 0.1 to 40% by weight, preferably from 5 to 30% by weight, morepreferably from 10 to 25% by weight and most preferably from 10 to 20%by weight of a solvent component.

The solvent components, including especially the particularly preferredsolvent combinations mentioned, can advantageously be supplemented withurea (generally from 0.5 to 3% by weight, based on the weight of thecolorant preparation) to further enhance the water-retaining effect ofthe solvent mixture.

The colorant preparations according to the invention may include furtherassistants of the type which are customary especially for aqueous inkjet inks and in the printing and coatings industry. Examples of suchassistants include preservatives such as for example1,2-benzisothiazolin-3-one (commercially available as Proxel® brandsfrom Avecia Lim.) and its alkali metal salts, glutaraldehyde and/ortetramethylolacetylenediurea, Protectols®, antioxidants,degasers/defoamers such as for example acetylenediols and ethoxylatedacetylenediols, which customarily contain from 20 to 40 mol of ethyleneoxide per mole of acetylenediol and may also have a dispersing effect,viscosity regulators, flow agents, wetters (eg wetting surfactants basedon ethoxylated or propoxylated fatty or oxo alcohols, propyleneoxide-ethylene oxide block copolymers, ethoxylates of oleic acid oralkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenyl phosphonates, alkyl phosphates, alkylphenylphosphates or preferably polyether siloxane copolymers, especiallyalkoxylated 2-(3-hydroxypropyl)hepta-methyltrisiloxanes, which generallyhave a block of from 7 to 20 and preferably of from 7 to 12 ethyleneoxide units and a block of from 2 to 20 and preferably of from 2 to 10propylene oxide units and may be present in the colorant preparations inamounts from 0.05 to 1% by weight), anti-settlers, luster improvers,lubricants, adhesion improvers, anti-skinning agents, delustrants,emulsifiers, stabilizers, hydrophobicizers, light control additives,hand improvers, antistats, bases such as for example triethanolamine oracids, specifically carboxylic acids such as for example lactic acid orcitric acid for regulating the pH. When such assistants are part of thepigment preparations according to the invention, their total amount isgenerally 2% by weight and especially 1% by weight, based on the weightof the colorant preparation.

Binder-free colorant preparations according to the invention customarilyhave a dynamic viscosity of from 1 to 7 mm²/sec, preferably of up to 5mm²/sec and especially from 1 to 3 mm²/sec. Binder-containing colorantpreparations according to the invention have a dynamic viscosity whichis generally in the range from 1 to 25 mm²/sec, preferably in the rangefrom 1 to 15 mm²/sec and especially in the range from 1 to 10 mm²/sec.

The surface tension of the binder-free or binder-containing colorantpreparations according to the invention is generally in the range from24 to 70 mN/m and especially in the range from 30 to 60 mN/m.

The pH of the colorant preparations according to the invention isgenerally in the range from 5 to 10 and preferably in the range from 7to 9.

Colorant preparations according to the invention which are based onundissolved colorant a1) are advantageously prepared as follows:

The colorant a1), for example in the form of an aqueous presscake, ismixed together with the dispersant c) in the presence of water anddispersed in a suitable apparatus. The resulting mixture is then groundin a mill to the desired particle size distribution (generally 1 μm onaverage, preferably 0.5 μm on average). After the desired colorantconcentration has been set by addition of solvent, water and optionallyfurther assistants, the preparation is filtered using a filtering meanswith fines removal in the range from 1 to 0.5 μm.

The particularly suitable starting material for preparations ofdissolved dye a2) is relatively highly concentrated dye solutions, forexample from 10 to 30% by weight liquid bands of dyes. These areoptionally demineralized and filtered (eg nanofiltration) before thedesired dye concentration is set.

A further aspect of the present invention is a process for printingsheetlike or three-dimensional substrates by the ink jet process usingthe colorant preparations according to the invention. To this end, thecolorant preparations according to the invention or the ink jet inksaccording to the invention are printed onto the substrate and the printobtained is then optionally fixed.

In the ink jet process, the typically aqueous inks are sprayed as smalldroplets directly onto the substrate. There is a continuous form of theprocess, in which the ink is pressed at a uniform rate through a nozzleand the jet is directed onto the substrate by an electric fielddepending on the pattern to be printed, and there is an interrupted ordrop-on-demand process, in which the ink is expelled only where acolored dot is to appear, the latter form of the process employingeither a piezoelectric crystal or a heated hollow needle (bubble orthermal jet process) to exert pressure on the ink system and so eject anink droplet. These techniques are described in Text. Chem. Color 19(1987), No. 8, 23-29, and 21 (1989), No. 6, 27-32.

The colorant preparations of-the invention are particularly useful asinks for the bubble jet process or the process employing a piezoelectriccrystal.

A further aspect of the present invention is a process for printingsubstrates by the ink jet process using the colorant preparationsaccording to the invention with subsequent fixing of the print. Thefixing can be achieved in various ways.

In one embodiment of the present invention, the actual printing with thecolorant preparations according to the invention by the ink jet processis followed by application of a binder in the form of a dispersion oremulsion, preferably in the form of an aqueous dispersion or emulsion,before effecting its curing, ie the chemical crosslinking of the binderitself, or before effecting the physical drying of the binder dispersionor emulsion.

In a further embodiment of the present invention, the actual printingwith the colorant preparations according to the invention by the ink jetprocess is followed by the lamination onto the print of a film, forexample of polyethylene terephthalate, to protect the print againstwater and light in particular.

The binder may in principle be applied using any process whereby astructured or unstructured coating can be produced. Examples of suchprocesses include in particular the techniques of screen printing,padding and spraying and other, uniform-coating techniques such asroller coating, offset printing, flexographic printing and casting.

The print may in principle be fixed using any kind of binder system, ifthe binder is applied after the actual printing.

It is possible to use radiation-curable, thermally curable or air-dryingbinders (ie chemically crosslinking binders) or physically drying binderdispersions or emulsions where the liquid phase (water or organicsolvent) evaporates.

Radiation-curable binders for the purposes of the present invention arebinders which are curable by radiation of high energy, ieelectromagnetic radiation especially from 220 to 450 nm, or electronbeams. It is possible to use not only free-radically but alsocationically polymerizable binder components and also mixtures thereof.Such binders are common knowledge and described, for example, inChemistry & Technology of UV & EB Formulation for Coatings, Inks &Paints, SITA Technology, London (1991), UV & EB Curing Formulation forPrinting Inks and Paints, SITA Technology, London (1984) and in the BASFpublication Vinyl Ethers, The Innovative Challenge (1997).

Examples of such radiation-curable binders include acrylate, vinyl andepoxy monomers, prepolymers and polymers and mixtures thereof.

Acrylate binders are especially prepolymers based on acrylate ormethacrylate, acrylate-based prepolymers being particularly preferred.

Preferred (meth)acrylate compounds generally contain from 2 to 20,especially from 2 to 10, in particular from 2 to 6, copolymerizable,ethylenically unsaturated double bonds. The number average molecularweight M_(n) is preferably ≦15,000, particularly preferably ≦5000, veryparticularly preferably within the range from 180 to 3000 g (determinedby gel permeation chromatography (GPC) using polystyrene as standard andtetrahydrofuran as mobile phase).

Examples of suitable (meth)acrylate compounds include (meth)acrylicesters and especially acrylic esters of polyhydric alcohols, especiallypolyhydric alcohols which, besides the hydroxyl groups, contain nofurther functional groups or at most ether groups. Examples of suchalcohols include dihydric alcohols, such as ethylene glycol, propyleneglycol and their higher condensed representatives, eg diethylene glycol,triethylene glycol, dipropylene glycol and tripropylene glycol, also1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol,1,2-hexanediol, 1,6-hexanediol, neopentylglycol, alkoxylated phenols andbisphenols such as for example ethoxylated bisphenol A,cyclohexanedimethanol. Also suitable are trihydric alcohols such as forexample glycerol, trimethylol-propane, 1,2,4-butanetriol,1,2,3-butanetriol, or trimethylol-ethane. It is finally also possible touse higher alcohols such as for example pentaerythritol,ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and thecorresponding alkoxylated, especially ethoxylated or propoxylated,derivatives.

Alkoxylation products are obtainable in a conventional manner byreacting the aforementioned alcohols with alkylene oxides, especiallyethylene oxide or propylene oxide. Useful catalysts include acidiccompounds,. for example SbCl₅, or else basic compounds, for exampleNaOCH₃.

Suitable methacrylate compounds further include polyester(meth)acrylates, polyester (meth)acrylates being the (meth)acrylicesters of polyesterols, which can be saturated or unsaturated.

Suitable polyesterols include for example polyesterols as are preparableby esterification of dicarboxylic acids and polycarboxylic acids,preferably dicarboxylic acids, with polyols. Preferred dicarboxylicacids include succinic acid, glutaric acid, adipic acid, sebacic acid,maleic acid, fumaric acid, phthalic acid, its isomers and hydrogenationproducts and also esterifiable derivatives, such as anhydrides ordimethyl esters or diethyl esters of the acids mentioned. Suitablepolyols include ethylene glycol, propylene glycol, and relatively highcondensation products such as diethylene glycol, triethylene glycol,dipropylene glycol, tripropylene glycol, moreover 1,3-propanediol,1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol,1,6-hexanediol and also polyalkylene glycols based on ethylene glycoland propylene glycol.

A suitable process for preparing the abovementioned (meth)acrylatecompounds is described, for example, in EP-A-279 303.

Epoxy (meth)acrylates and urethane (meth)acrylates are further useful(meth)acrylate compounds. Epoxy (meth)acrylates are obtainable forexample by reaction of epoxidized olefins or mono-, di- or polyglycidylethers, such as bisphenol A diglycidyl ether, with (meth)acrylic acid.Urethane (meth)acrylates are especially reaction products ofhydroxyalkyl (meth)acrylates with poly- or diisocyanates.

Melamine (meth)acrylates and silicone (meth)acrylates are furthersuitable (meth)acrylate compounds. (Meth)acrylate compounds may bemodified to be nonionic—by attachment of amino groups, for example—orionic—by attachment of acid groups or ammonium groups, for example—andbe used in the form of preferably aqueous dispersions or emulsions(known as such from EP-A 0 704 469 and EP-A 0 012 339).

Furthermore, the (meth)acrylate compounds may be adjusted to the desiredviscosity by means of reactive diluents. Examples of suitable reactivediluents include vinyl monomers, especially N-vinyl compounds such asN-vinylpyrrolidone, N-vinylcaprolactam and N-vinylformamide, and vinylethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether,amyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether,octadecyl vinyl ether and cyclohexyl vinyl ether, ethylene monoglycolvinyl ether, ethylene monoglycol divinyl ether, diethylene glycolmonovinyl ether, diethylene glycol divinyl ether, triethylene glycolmonovinyl ether, triethylene glycol divinyl ether, tetraethylene glycolmonovinyl ether, tetraethylene glycol divinyl ether, propylene glycoldivinyl ether, polyethylene glycol divinyl ether, ethylene glycol butylvinyl ether, triethylene glycol methyl vinyl ether, polyethylene glycolmethyl vinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanedioldivinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinylether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanoldivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropanedivinyl ether, aminopropyl vinyl ether, diethylaminoethyl vinyl ether,and polytetrahydrofuran divinyl ether, vinyl esters, such as vinylacetate, vinyl propionate, vinyl stearate and vinyl laurate, andaromatic vinyl compounds, such as vinyltoluene, styrene, 2-butylstyrene,4-butylstyrene and 4-decylstyrene, and also acrylate monomers, such asphenoxyethyl acrylate, tert-butylcyclohexyl acrylate, 1,6-hexanedioldiacrylate, tripropylene glycol diacrylate and trimethylolpropanetriacrylate.

Vinyl compounds may also be used directly as cationically polymerizablebinders.

As radiation-curable binders there may further be used epoxy compounds,such as cyclopentene oxide, cyclohexene oxide, epoxidized polybutadiene,epoxidized soybean oil, 3′,4′-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate and glycidyl ethers, eg 1,4-butanedioldiglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol Adiglycidyl ether and pentaerythritol diglycidyl ether, in which casecationically polymerizable monomers, for example unsaturated aldehydesand ketones, dienes such as butadiene or isoprene, aromatic vinylcompounds such as styrene, N-substituted vinylamines such asvinylcarbazole and cyclic ethers such as tetrahydrofuran, may likewisebe used as well.

In the particular case where the binder is to be cured by means of UVradiation, it is advisable to apply the binder to the print togetherwith a photoinitiator to initiate the polymerization.

Examples of photoinitiators which are suitable for free-radicalphotopolymerizations include benzophenone and benzophenone derivativessuch as 4-phenylbenzophenone and 4-chlorobenzophenone, acetophenonederivatives such as 1-benzoylcyclohexan-1-ol,2-hydroxy-2,2-dimethylacetophenone and2,2-dimethoxy-2-phenylacetophenone, benzoin and benzoin ethers such asmethyl benzoin ether, ethyl benzoin ether and butyl benzoin ether,benzil ketals such as benzil dimethyl ketal,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphineoxide and bisacylphosphine oxides.

Examples of photoinitiators which are suitable for cationicphotopolymerizations include aryldiazonium salts such as4-methoxybenzenediazonium hexafluorophosphate, benzenediazoniumtetrafluoroborate and toluenediazoniumtetrafluoroarsenate, aryl iodoniumsalts such as diphenyliodonium hexafluoroarsenate, arylsulfonium saltssuch as triphenylsulfonium hexafluorophosphate, benzenesulfoniumhexafluorophosphate, toluenesulfonium hexafluorophosphate andbis[4-diphenylsulfoniophenyl] sulfide bishexafluorophosphate, disulfonessuch as diphenyl disulfone and phenyl 4-tolyl disulfone,diazodisulfones, imidotriflates, benzoin tosylates, isoquinolinium saltssuch as N-ethoxyisoquinolinium hexafluorophosphate, phenylpyridiniumsalts such as N-ethoxy-4-phenylpyridinium hexafluorophosphate,picolinium salts such as N-ethoxy-2-picolinium hexafluorophosphate,ferrocenium salts and titanocenes.

Where the presence of a photoinitiator is required, it is generally usedin amounts from 0.1 to 10% by weight, preferably from 0.1 to 8% byweight, based on the weight of the binder.

The subsequent curing of the binder, ie the fixing of the print, can beeffected in a conventional manner using high energy radiation whenradiation-curable binders are used. To this end, the print is irradiatedeither with electrons (electron beam curing) under an inert gas(nitrogen, for example) or with high energy electromagnetic radiation,preferably in the wavelength range from 220 to 450 nm. The lightintensities which are selected have to be adapted to the rate-of curingto avoid any degradation of the colorant. In the case of a lamp poweroutput of from 210 to 240 W/cm, the rate of curing can be up to 100m/min, depending on the concentration and type of photoinitiator.

Thermally curable binders are typically crosslinked by polycondensationor polyaddition reactions. These binders are likewise common knowledgeand described for example in Glasurit-Handbuch Lacke und Farben der BASFFarben und Fasern AG, Vincentz Verlag, Hannover (1984) and in LackharzeChemie, Eigenschaften, Anwendungen, Karl Hanser Verlag, Munich/Vienna(1996).

It is particularly useful to use, for example,polycondensation-crosslinkable binders based on acrylates which containmethylol groups.

Examples of preferred systems include mixtures of from 1 to 10% byweight of N-methylol (meth)acrylamide or its C₁-C₄-alkyl ethers and, ifdesired, monomers which contain halohydrin groups such as2-hydroxy-3-chloropropylene acrylate and

from 90 to 99% by weight of comonomers selected, for example, from thegroup consisting of butadiene, styrene, (meth)acrylic acid,(meth)acrylonitrile, (meth)acrylic and vinyl esters having up to 12carbon atoms, vinyl chloride and N-vinylpyrrolidone, as described forexample in DE-A 16 19 656.

Acrylic acid derivatives which contain methylol groups bring aboutadditional crosslinking in the presence of acids or of compounds whichdetach protons when heated, such as ammonium phosphates.

Examples of air-drying binders where aliphatic double bonds areoxidatively crosslinked by the action of atmospheric oxygen are dryingoils such as linseed oil, wood oil and safflower oil.

Useful thermally curable binders further include binders which are basedon polyurethane prepolymers and which likewise crosslink bypolycondensation.

If the binder, as is preferred in the present invention, is applied inthe form of a dispersion or emulsion to the substrates printed with thecolorant preparations of the invention, the binder content of thesedispersions or emulsions is within the range from 10 to 60% by weight,preferably within the range from 10 to 30% by weight. It is customary touse sufficient binder to form a protective film on the substrate whichis from about 1 to 30 μm in thickness when dry.

The areas printed by the ink jet process-are customarily heat treated tofix and develop the dyes. The heating can be effected for example usingsteam or hot air. A customary temperature range is from 160 to 180° C.for from 5 to 8 minutes. In the case of hot air, it is advisable totreat the printed textile at from 180 to 200° C. for 1 minute.

In a further embodiment of the present invention, development iseffected by the action of IR or microwave radiation or of high energyelectromagnetic radiation.

In a further version of the present invention, dispersions of theabovementioned radiation-curable, thermally curable or air oxidationdrying binders are added to the colorant preparations of the presentinvention or to the inks of the present invention before printing. Thepresent invention further provides colorant preparations comprisingdispersions of the abovementioned binders. The present invention furtherprovides in addition a process for printing substrates by the ink jetprocess using the colorant preparations of the present invention whichwere defined at the beginning to which a binder has been added beforeprinting.

Useful substrate materials include:

cellulosics such as paper, paperboard, cardboard, wood and woodbase,

metallic materials such as foils, sheets or workpieces composed ofaluminum, iron, copper, silver, gold, zinc or alloys thereof,

silicatic materials such as glass, porcelain and ceramic that maylikewise be coated,

polymeric materials of any kind such as polystyrene, polyamides,polyesters, polyethylene, polypropylene, melamine resins, polyacrylates,polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride,polyvinyl alcohols, polyvinyl acetates, polyvinylpyrrolidones andcorresponding copolymers and block copolymers, biodegradable polymersand natural polymers such as gelatin,

textile materials such as fibers, yarns, threads, knits, wovens,nonwovens and garments composed of polyester, modified polyester,polyester blend fabrics, cellulosics such as cotton, cotton blendfabrics, jute, flax, hemp and ramie, viscose, wool, silk, polyamide,polyamide blend fabrics, polyacrylonitrile, triacetate, acetate,polycarbonate, polypropylene, polyvinyl chloride, polyester microfibersand glass fiber fabric,

leather—both natural and artificial—in the form of smooth leather, nappaleather or suede leather,

comestibles and cosmetics.

The colorant preparations according to the invention are useful as inkjet inks having altogether advantageous application properties,especially good start-of-print performance and good sustained useperformance (kogation) and also, especially when the particularlypreferred solvent combination is used, good dry time and produce printedimages of high quality, ie of brilliance and depth of shade and alsohigh rub-, light-, water- and wetrubfastness. They are particularlyuseful for printing coated and uncoated paper and also textile.

A further embodiment of the present invention provides substrates,especially textile substrates, which have been printed by one of theabovementioned processes according to the invention and are notable forparticularly crisply printed pictures or drawings.

It has also been determined that the colorant preparations according tothe invention are particularly useful for ink jet printing by thetransfer process on using disperse dye a1). In the transfer printingprocess, first the image is printed onto a transfer material, forexample onto paper, especially paper from Coldenhove (Netherlands) andCam Tenero (Switzerland) specifically manufactured for this process, andtransferred from there, by means of heat, to substrates, for example tosubstrates composed of textile. A further embodiment of the presentinvention accordingly provides a process for printing substrates,preferably textile substrates, by the transfer printing process usingthe colorant preparations according to the invention and alsosubstrates, preferably textile substrates, printed by the transferprinting process using the colorant preparations according to theinvention. The colorant preparations for the transfer printing processare preferably produced on the basis of a disperse dye. Particularpreference is given to preparing the inks for the transfer printingprocess on the basis of the following colorants:

Disperse Yellow 54,

Disperse Red 11, 60,

Disperse Blue 72, 289, 326, 332, 347, 359;

Disperse Violet 17.

The colorant preparations according to the invention are lastly veryuseful as an ink for fountain pens or for preparing inks for fountainpens. A further aspect of the present invention is therefore the use ofthe colorant preparations according to the invention as or in inks forfountain pens and also inks for fountain pens comprising the colorantpreparations according to the invention. The colorant preparations caneither be filled into common ink bottles or ink cartridges immediatelyafter production or else be diluted with common additives.

The inks thus obtainable are notable for an excellent performanceprofile. There may be mentioned by way of example an excellent dry timeand the observation that the inks flow freely from the line, ensuringvery uniform application to paper for example.

EXAMPLES Preparation of Inventive Colorant Preparations

1st Step: Preparation of Dispersant C2-A

Dispersant C2-A was prepared in the same way as “Dispersant 4” in U.S.Pat. No. 5,186,846.

A cracker fraction of the following composition (Table 1a) was used as astarting material: TABLE 1A % by weight in aromatics fractionNaphthalene 54.60 2-Methylnaphthalene 14.00 1-Methylnaphthalene 8.30Indene 8.40 Biphenyl 3.20 Methylindene 1.95 Acenaphthene 1.70 Fluorene1.30 Indan 1.22 Phenanthrene 1.10 Methylindan (mixed isomers) 1.13Ethylnaphthalene (mixed isomers) 0.90 para- and meta-Xylene 0.80Tetralin 0.80 Styrene 0.60

128 g of the cracker fraction were mixed with 25 g of benzoic acid andheated to 90° C. in a kettle. 107 g of oleum having an SO₃ content of65% by weight were then added over a period of 2 hours, during whichcare was taken to ensure that the temperature did not exceed 95° C. Oncompletion of the oleum addition the batch was heated to 140° C. andstirred at 140° C. for about 3½ hours. This was followed by cooling to80° C., and the addition of 150 ml of water, followed by 50 g of 30% byweight formalin solution. The ensuing condensation reaction wascontinued at 100° C. for 8 hours.

½ l of water was then added, followed by 131 g of 50% by weight aqueoussodium hydroxide solution. The mixture was stirred at 90° C. for onehour. A further 365 ml of water were then added before a pH of 8.4 wasset with 20% by weight H₂SO₄. The C2-B product was lastly isolated byspray drying in a spray tower.

The product comprised the following characteristic parameters: α-:β-naphthalenesulfonic acid 1:4.5, Na₂SO₄ content: 1.5% by weight.

2nd Step: Preparation of Mix Component

In a dissolver, 12.5 g of Tectilon® Blue Base 6G (commercially availablefrom Ciba Specialties) were mixed with 6.25 g of Pluriol E 400®(commercially available from BASF Aktiengesellschaft), C2-A dispersant,0.3 g of biocide A and 0.4 g of biocide B with 0.5 g of triethanolamineand made up with 67.55 ml of demineralized water. This mixture was ballmilled for 5 hours to a maximum particle diameter of 1 μm.

The composition of these and further, similarly prepared mix componentsis evident from Table 2. All input materials are reported in grams.TABLE 2 Input material Turquoise Yellow Red Blue 1 Blue 2 InthrathermBlue 12.5 P-305 NT Quinone Blue PM 12.5 Palanil Red BFW-L 15 Palanil ®Yellow 3GE 15 Tectilon ® Blue 12.5 Pluriol E 400 ® 6.25 15 7.5 12.5 12.5C2-A 12.5 7.5 15 6.25 6.25 Biocide A 0.3 0.4 0.4 0.3 0.3 Biocide B 0.40.5 0.5 0.4 0.4 Triethanolamine 0.5 0.5 0.5 0.5 0.5 DM water 67.55 61.161.1 67.55 67.55

3rd Step: Formulation of a Highly Concentrated Ink

In a beaker, 32.0 g of a turquoise mix component prepared according to2. were admixed with 5.0 g of compound I a

and further mixed with 10 g of glycerol, 3 g of Pluriol E 400®, 1 g ofPluriol E 4000®, 0.5 g of Biocide D, 0.1 g of triethanolamine, 0.2 g ofTego Wet 260® and 48.2 ml of DM water.

The compositions of further inks are evident from Table 3 (seehereinbelow). TABLE 3 Formulations of inks Ink 1 Ink 2 Ink 3 Ingredient(turquoise) (turquoise) (turquoise) Mix component 32.0 32.0 32.0Compound Ia 5.0 5.0 5.0 Pluriol E 400 3.0 3.0 3.0 Pluriol E 4000 1.0 1.01.0 Glycerol 10.0 1,2-Pentanediol 10.0 1,2-Propanediol 10.0 Biocide D0.5 0.5 0.5 Tego Wet 260 0.2 0.2 0.2 Triethanolamine 0.1 0.1 0.1 DMwater [ml] 48.2 48.2 48.2 Viscosity [mm²/s] 2.537 2.814 2.688

All components in g, unless otherwise stated. The viscosities weredetermined in accordance with DIN 51662 using an Ubbelohde viscometer.

Biocide A is a 50% by weight aqueous solution of glutaraldehyde.

Biocide B is a 4% by weight aqueous solution oftetramethylolacetylenediurea.

Biocide C is a 20% by weight solution of 1,2-benzisothiazolon-3-one inaqueous ethylene glycol.

Biocide D is a 10% by weight solution of 1,2-benzisothiazolon-3-one inaqueous propylene glycol.

The wetting agent is 2-(3-hydroxypropyl)heptamethyltrisiloxane,initially ethoxylated and then propoxylated (11 mol of ethylene oxide/5mol of propylene oxide).

4th Step

The ink obtained in step 3 was printed onto A3 paper using an EPSON 3000Stylus Color thermal head printer. The prints obtained had excellentline crispness. There was no nozzle failure after 40 sheets of paper,nor after 5 m² of printing. The prints obtained after the ink was leftto stand at room temperature for 6 days were likewise excellent and freeof stripes.

Inks 4 and 5 and also comparative examples V1 to V4 (dilute inks)

The inks recited in Table 4 were formulated in a beaker starting fromthe mix components Turquoise and Blue 2 (see step 2).

The comparative examples utilized the following urea derivatives

in place of I a. TABLE 4 Compositions of dilute inks Ingredients Ink 4Ink 5 Ink V1 Ink V2 Ink V3 Ink V4 Turquoise 10.0 10.0 10.0 mix componentBlue I mix 10.0 10.0 10.0 component Glycerol 8.0 8.0 8.0 8.0 8.0 8.0Pluriol 3.0 3.0 3.0 3.0 3.0 3.0 E 400 ® Pluriol 1.0 1.0 1.0 1.0 1.0 1.0E 4000 ® Dispersant 2.0 2.0 2.0 2.0 2.0 2.0 C2-A Tego Wet 0.1 0.1 0.10.1 0.1 0.1 260 ® Biocide D 0.48 0.48 0.48 0.48 0.48 0.48Triethanolamine 0.05 0.05 0.05 0.05 0.05 0.05 DM water 85.37 85.37 85.3785.37 85.37 85.37 [ml] Intermediate 100.0 100.0 100.0 100.0 100.0 100.0total I a 5.0 5.0 II a.1 5.0 5.0 II b.1 5.0 5.0 Grand total 105.0 105.0105.0 105.0 105.0 105.0

All amounts reported in g, unless otherwise stated.

The inks were printed onto A3 paper of the Coldenhove HTR 2000 brandusing an Epson 3000 Stylus Color printer. Print quality was good in eachcase.

The inks were aged at 60° C. for 5 days before the printing trials wererepeated.

The prints prepared using the inks according to the invention exhibitedvery good contours and uniformly brilliantly colored areas.

The prints prepared using the comparative inks appeared less uniform andcontours were not as good. Examined under a microscope at 75-foldmagnification, the colorant was seen to be present in the form ofcomparatively large circular crystals when the V2 and V4 comparativeinks were used. When the V1 and V3 comparative inks were used, the onsetof phase separation was observed.

Examples of the Use as a Fountain Pen Ink

The 4, V1 and V2 inks were each filled into ink cartridges and writtenonto papers of the brands Coldenhove HTR 2000, Neusiedler Color Copy,Epson Super Fine Paper®, HP Premium InkJet Glossy Paper® and Motiv CopyPaper using a Parker Frontier® fountain pen. Straight lines were drawnfor comparison. The lines drawn using ink 4 according to the inventionhad a completely uniform width, while the V1 and V2 comparative inks didnot exhibit uniform width and even showed some interruptions on MotivCopy Paper.

1: Colorant preparations comprising a) at least one colorant selectedfrom sparingly water-soluble colorants a1) and water-soluble dyes a2),b) water, c) at least one dispersant in the case of substantiallywater-insoluble or sparingly water-soluble colorants a1), and d) atleast one compound of formula I

where R¹ and R² are independently selected from hydrogen, C₁-C₄-alkyland CH₂—O—R³, where R³ is hydrogen or C₁-C₄-alkyl. 2: Colorantpreparations as claimed in claim 1, wherein R¹ and R² are the same. 3:Colorant preparations as claimed in claim 1, wherein R¹ and R² are eachmethyl or hydrogen. 4: Colorant preparations as claimed in claim 1,wherein said dispersant c) comprises arylsulfonic acid-formaldehydecondensation products. 5: Colorant preparations as claimed in claim 1,comprising said colorant a1); wherein said colorant a1) is a dispersedpigment, a dispersed disperse dye or a solvent dye. 6: A process forprinting substrates by the ink jet process, which comprises usingcolorant preparations as claimed in claim
 1. 7: A process as claimed inclaim 6, wherein the print is fixed after the actual printing. 8: Aprocess as claimed in claim 7, wherein a binder in the form of adispersion or emulsion is applied to the printed substrate after theactual printing. 9: A process as claimed in claim 7, wherein adispersion or emulsion of a thermally curable binder, of an air-dryingbinder or of a radiation-curable binder, said dispersion or emulsionoptionally further comprising a photoinitiator, or a physically dryingbinder dispersion or emulsion is applied for fixation. 10: A process asclaimed in claim 7, wherein said binder is cured by the action of IRradiation, electron beam radiation or high energy electromagneticradiation. 11: A process as claimed in claim 7, wherein a film islaminated onto the print after the actual printing. 12: A process forprinting substrates, which comprises: transfer printing the colorantpreparations of claim 1 to the substrate. 13: A process for printingsubstrates by the ink jet process using colorant preparations as claimedin claim 1, which comprises adding a binder to the colorant preparationsbefore printing. 14: Substrates printed by a process as claimed in claim6. 15: The use of colorant preparations as claimed in claim 1 as or ininks for fountain pens. 16: A process for printing one or more textilesubstrate, which comprises: transfer printing the colorant preparationas claimed in claim 1 to the textile substrate. 17: A fountain pen,which comprises: the colorant preparation as claimed in claim 1 or anink comprising the colorant preparation.